US4966949A - Process for increasing the molecular weight of a polyamide with p containing catalyst - Google Patents

Process for increasing the molecular weight of a polyamide with p containing catalyst Download PDF

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Publication number
US4966949A
US4966949A US07/262,936 US26293688A US4966949A US 4966949 A US4966949 A US 4966949A US 26293688 A US26293688 A US 26293688A US 4966949 A US4966949 A US 4966949A
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United States
Prior art keywords
acid
polyamide
molecular weight
catalyst
group
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US07/262,936
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English (en)
Inventor
Robert C. Wheland
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Invista North America LLC
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EI Du Pont de Nemours and Co
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Priority to US07/262,936 priority Critical patent/US4966949A/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, DE. A CORP. OF DE. reassignment E. I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, DE. A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: WHELAND, ROBERT CLAYTON
Priority to EP89909640A priority patent/EP0439470B1/en
Priority to SU894895302A priority patent/RU2066331C1/ru
Priority to DE68919228T priority patent/DE68919228T2/de
Priority to JP1509052A priority patent/JP2888573B2/ja
Priority to PCT/US1989/003464 priority patent/WO1990004614A1/en
Priority to IN862/CAL/89A priority patent/IN171375B/en
Priority to TR89/0808A priority patent/TR24062A/xx
Priority to AR89315237A priority patent/AR243912A1/es
Priority to CA002001090A priority patent/CA2001090A1/en
Publication of US4966949A publication Critical patent/US4966949A/en
Application granted granted Critical
Priority to LVP-93-349A priority patent/LV10469B/xx
Assigned to INVISTA NORTH AMERICA S.A.R.L. reassignment INVISTA NORTH AMERICA S.A.R.L. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: E. I. DU PONT DE NEMOURS AND COMPANY
Assigned to JPMORGAN CHASE BANK, N.A. reassignment JPMORGAN CHASE BANK, N.A. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INVISTA NORTH AMERICA S.A.R.L. F/K/A ARTEVA NORTH AMERICA S.A.R.
Anticipated expiration legal-status Critical
Assigned to INVISTA NORTH AMERICA S.A.R.L. (F/K/A ARTEVA NORTH AMERICA S.A.R.L.) reassignment INVISTA NORTH AMERICA S.A.R.L. (F/K/A ARTEVA NORTH AMERICA S.A.R.L.) RELEASE OF U.S. PATENT SECURITY INTEREST Assignors: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT (F/K/A JPMORGAN CHASE BANK)
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C08G69/18—Anionic polymerisation
    • C08G69/20—Anionic polymerisation characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes

Definitions

  • This invention relates to increasing the molecular weight of a polyamide by using a designated catalyst.
  • n 1, 2 or 3
  • R is a mono-, di-, or trivalent organic radical depending on the value of n.
  • Example 10 shows the use of a weakly activating substituent (p-PO 3 H 2 C 6 H 4 --). The results, however, as stated in the patent clearly show that this example gives results which are only slightly better than phenylphosphonic acid as measured by the relative viscosity of the final product. There is no indication from the Examples that moderate or strongly activating groups would have a significant effect on the rate of reaction.
  • Example 8 shows the use of the weakly activating substituents CH 3 -- and C 6 H 5 --; as stated in this Example, the results as obtained are similar to the results obtained using a similar amount of phenylphosphinic acid. There is no indication from the Examples that moderate or strongly activating groups would have a significant effect on the rate of reaction.
  • the process of the instant invention is an improved process for increasing the molecular weight of a polyamide, comprising heating the polyamide in the presence of a catalyst to effect a desired increase in molecular weight
  • Derivatives of substituted phenylphosphonic or phenylphosphinic acids which are easily hydrolyzed to the parent acid under the conditions of the polymerization reaction, such as the mono or diesters or the mono or diamides, are suitable for the process of this invention.
  • the catalysts used in the process of this invention are either available chemicals or chemicals which can be readily produced in accordance with known processes.
  • a preferred process for making the phosphonic acid catalysts comprises photochemically reacting the appropriate halide with an alkyl phosphite (Arbuzov reaction) and hydrolyzing the phosphonite ester so produced (See, for example, J. B. Plumb et al., J. Org. Chem., 27, 4711 (1962)).
  • a preferred process for making the phosphinic acid catalysts comprises reacting the appropriate aromatic with phosphorous trichloride in the presence of catalyst and hydrolyzing the aromatic phosphorous dichloride so produced (See, for example, Houben-Weyl, "Methoden Der Organischen Chemie", page 294 and following).
  • polyamides used in the process of this invention are conventional.
  • Polyamides are condensation products that contain recurring amide groups as integral parts of the main polymer chains.
  • Linear polyamides are formed from condensation of bifunctional monomers.
  • R' and R" are linear or branched alkylene groups containing from 2 to 12 carbon atoms; R" may also be aromatic groups such as phenylene or naphthalyene and n represents the degree of polymerization or the number of recurring groups in the polymer chain.
  • the value of n for a given polyamide such as nylon-6,6 should be such that the molecular weight is about 15,000 (40 RV).
  • Preferred polyamides are nylons, including but not limited to nylon-6 and nylon-6,6.
  • nylon-6,6 is the most preferred species.
  • the temperature range for the melting point of the polyamides to be used in the process of this invention is up to 360° C.
  • the catalysts of this invention are preferably used at or above the melting temperature of the polyamide, the upper limit being generally dictated by the decomposition temperature of the polymer. In the case of nylon-6,6, the operating temperature is about 265°-300° C., preferably 270°-295° C.
  • the catalysts can also be employed below the melting temperature of the polymer, preferably at least 15° C. below the melting point to avoid working with a hard to handle, sticky mass.
  • the preferred operating temperature for employing the catalyst below the melting point is 170°-245° C.
  • the reaction time is sufficient to obtain the desired increase in molecular weight.
  • the increase in molecular weight which is desired is usually measured by the change in relative viscosity and can range from 10 to 600. This represents a change in molecular weight of from about 15,000 to about 45,000.
  • the preferred reaction time being generally about 1 to 60 minutes for the liquid phase reaction.
  • the preferred reaction time being generally >15 minutes.
  • the amount of phosphonic and/or phosphinic catalysts employed in the reaction is sufficient to obtain a catalytic effect, the preferred concentration of phosphonic or phosphinic acid, for example, being about ⁇ 0.1 gram moles of catalyst per million grams of polyamide.
  • the reaction is conducted preferably in the absence of air, for example, in the presence of an inert gas such as nitrogen, helium or argon.
  • Both the catalysts of this invention and comparative catalysts are tested in a thin film polymerizer.
  • This is an apparatus for conducting small scale nylon polymerizations under controlled conditions of temperature, water vapor pressure, and reaction time; in principal all the factors necessary for the determination of amidation kinetics.
  • a low molecular weight nylon sample is melted under its equilibrium steam pressure, the steam pressure is reduced, and the reaction quenched before a new equilibrium is attained.
  • By relative viscosity analysis one can then determine how fast the sample approached the new equilibrium and thus amidation kinetics and catalytic factors.
  • An important feature of the thin film polymerizer is that the nylon samples are melted in broad cups, allowing the melt to spread out as a pool 2 mm deep that can respond rapidly to changes in steam pressure.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
US07/262,936 1988-10-20 1988-10-20 Process for increasing the molecular weight of a polyamide with p containing catalyst Expired - Lifetime US4966949A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US07/262,936 US4966949A (en) 1988-10-20 1988-10-20 Process for increasing the molecular weight of a polyamide with p containing catalyst
EP89909640A EP0439470B1 (en) 1988-10-20 1989-08-17 Process for increasing the molecular weight of a polyamide
SU894895302A RU2066331C1 (ru) 1988-10-20 1989-08-17 Способ повышения молекулярного веса полиамида
DE68919228T DE68919228T2 (de) 1988-10-20 1989-08-17 Verfahren zur erhöhung des molekulargewichts eines polyamids.
JP1509052A JP2888573B2 (ja) 1988-10-20 1989-08-17 ポリアミドの分子量の増加方法
PCT/US1989/003464 WO1990004614A1 (en) 1988-10-20 1989-08-17 Process for increasing the molecular weight of a polyamide
IN862/CAL/89A IN171375B (en)van) 1988-10-20 1989-10-18
AR89315237A AR243912A1 (es) 1988-10-20 1989-10-20 Procedimiento para aumentar el peso molecular de una poliamida.
TR89/0808A TR24062A (tr) 1988-10-20 1989-10-20 Bir poliamidin molekuel agirliginin artirilmasi icin usul
CA002001090A CA2001090A1 (en) 1988-10-20 1989-10-20 Process for increasing the molecular weight of a polyamide
LVP-93-349A LV10469B (en) 1988-10-20 1993-05-14 Process for increasing the molecular weight of a polyamide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07/262,936 US4966949A (en) 1988-10-20 1988-10-20 Process for increasing the molecular weight of a polyamide with p containing catalyst

Publications (1)

Publication Number Publication Date
US4966949A true US4966949A (en) 1990-10-30

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US07/262,936 Expired - Lifetime US4966949A (en) 1988-10-20 1988-10-20 Process for increasing the molecular weight of a polyamide with p containing catalyst

Country Status (11)

Country Link
US (1) US4966949A (en)van)
EP (1) EP0439470B1 (en)van)
JP (1) JP2888573B2 (en)van)
AR (1) AR243912A1 (en)van)
CA (1) CA2001090A1 (en)van)
DE (1) DE68919228T2 (en)van)
IN (1) IN171375B (en)van)
LV (1) LV10469B (en)van)
RU (1) RU2066331C1 (en)van)
TR (1) TR24062A (en)van)
WO (1) WO1990004614A1 (en)van)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5116919A (en) * 1990-12-05 1992-05-26 E. I. Du Pont De Nemours And Company Process for increasing the relative viscosity of polyamides with reduced thermal degradation
US5142000A (en) * 1991-08-28 1992-08-25 E. I. Du Pont De Nemours And Company Process for increasing polyamide molecular weight with organophosphonic acid or ester catalysts in the presence of alumina-containing titanium dioxide
WO1997045471A1 (en) * 1996-05-31 1997-12-04 E.I. Du Pont De Nemours And Company Linear very high molecular weight polyamides and process for producing them
US6169162B1 (en) 1999-05-24 2001-01-02 Solutia Inc. Continuous polyamidation process
US6504004B2 (en) 2000-01-20 2003-01-07 E. I. Du Pont De Nemours And Company Polyamide chain extension process and related polyamide product
US6866930B2 (en) 2000-01-20 2005-03-15 Invista North America S.A.R.L. Polyamide chain extension process and functionalized polyamides produced thereby
US20190322805A1 (en) * 2018-04-18 2019-10-24 Invista North America S.A R.L. Flame-retardant polyamide composition
WO2025022210A1 (en) 2023-07-27 2025-01-30 Inv Performance Materials, Llc Polyamide yarn with improved fatigue resistance and the use thereof for the manufacture of tire cord

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5543495A (en) * 1994-03-08 1996-08-06 E. I. Du Pont De Nemours And Company Process for increasing the molecular weight of polyamides and other condensation polymers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3365428A (en) * 1965-03-25 1968-01-23 Celanese Corp Polymerization of polyamide-precursor salt in the presence of a phosphinic acid
US3763113A (en) * 1965-06-23 1973-10-02 H Burrows Polyamides
US4912175A (en) * 1988-08-01 1990-03-27 E. I. Du Pont De Nemours And Company Process for in creasing polyamide molecular weight with P containing catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3365428A (en) * 1965-03-25 1968-01-23 Celanese Corp Polymerization of polyamide-precursor salt in the presence of a phosphinic acid
US3763113A (en) * 1965-06-23 1973-10-02 H Burrows Polyamides
US4912175A (en) * 1988-08-01 1990-03-27 E. I. Du Pont De Nemours And Company Process for in creasing polyamide molecular weight with P containing catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
U.S. Pat. No. 3,306,875; cols 1 2, 35 36. *
U.S. Pat. No. 3,306,875; cols 1-2, 35-36.

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5116919A (en) * 1990-12-05 1992-05-26 E. I. Du Pont De Nemours And Company Process for increasing the relative viscosity of polyamides with reduced thermal degradation
US5142000A (en) * 1991-08-28 1992-08-25 E. I. Du Pont De Nemours And Company Process for increasing polyamide molecular weight with organophosphonic acid or ester catalysts in the presence of alumina-containing titanium dioxide
WO1997045471A1 (en) * 1996-05-31 1997-12-04 E.I. Du Pont De Nemours And Company Linear very high molecular weight polyamides and process for producing them
US5698658A (en) * 1996-05-31 1997-12-16 E. I. Du Pont De Nemours And Company Linear very high molecular weight polyamides and process for producing them
US6169162B1 (en) 1999-05-24 2001-01-02 Solutia Inc. Continuous polyamidation process
US6504004B2 (en) 2000-01-20 2003-01-07 E. I. Du Pont De Nemours And Company Polyamide chain extension process and related polyamide product
US6866930B2 (en) 2000-01-20 2005-03-15 Invista North America S.A.R.L. Polyamide chain extension process and functionalized polyamides produced thereby
US20190322805A1 (en) * 2018-04-18 2019-10-24 Invista North America S.A R.L. Flame-retardant polyamide composition
WO2025022210A1 (en) 2023-07-27 2025-01-30 Inv Performance Materials, Llc Polyamide yarn with improved fatigue resistance and the use thereof for the manufacture of tire cord
WO2025022209A1 (en) 2023-07-27 2025-01-30 Inv Performance Materials, Llc Polyamide industrial yarn with improved thermo-mechanical properties
WO2025022208A1 (en) 2023-07-27 2025-01-30 Inv Performance Materials, Llc Polyamide for making polyamide yarn having improved mechanical and thermo-mechanical properties

Also Published As

Publication number Publication date
RU2066331C1 (ru) 1996-09-10
LV10469B (en) 1996-02-20
LV10469A (lv) 1995-02-20
EP0439470B1 (en) 1994-11-02
IN171375B (en)van) 1992-09-26
DE68919228D1 (de) 1994-12-08
WO1990004614A1 (en) 1990-05-03
AR243912A1 (es) 1993-09-30
TR24062A (tr) 1991-02-22
JP2888573B2 (ja) 1999-05-10
JPH04501126A (ja) 1992-02-27
EP0439470A1 (en) 1991-08-07
DE68919228T2 (de) 1995-03-23
CA2001090A1 (en) 1990-04-20

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